CN1606573A - Processes for production of powdered fluororesins bearing curable functional groups and coating compositions containing the same - Google Patents

Processes for production of powdered fluororesins bearing curable functional groups and coating compositions containing the same Download PDF

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Publication number
CN1606573A
CN1606573A CNA028255992A CN02825599A CN1606573A CN 1606573 A CN1606573 A CN 1606573A CN A028255992 A CNA028255992 A CN A028255992A CN 02825599 A CN02825599 A CN 02825599A CN 1606573 A CN1606573 A CN 1606573A
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solution
dispersion liquid
functional group
fluorinated copolymer
powder coating
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CN1310958C (en
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山内优
石田彻
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/10—Removal of volatile materials, e.g. solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8074—Lactams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

It is to provide a production process by which gelation can be prevented, in a case where a solvent is removed from a curable fluororesin to obtain a chief material resin, and then coating additives such as a curing agent are mixed to produce a powder coating composition, or in a case where a curable fluororesin, a curing agent and various additives are dissolved or dispersed in a solvent to prepare a raw material solution, and the solvent is removed from the raw material solution to directly produce a powder coating material. To a solution or dispersion of a curable fluorinated copolymer (A), a gelation inhibitor (B) is added, followed by mixing, or a gelation inhibitor (B), a curing agent (C) and as the case requires, various additives are added, followed by mixing, and the solution or dispersion is supplied to a thin-film vacuum evaporator to remove the solvent.

Description

Have the fluorine resin powder of solidified nature functional group and the manufacture method of coating composition thereof
Technical field
The present invention relates to utilize the method for film vacuum-evaporation manufactured fluorine resin powder and coating composition thereof.More specifically relate under than higher temperature condition, utilize the film vacuum-evaporator unit to remove under the situation of desolvating, be difficult to cause the gelation of resin, in addition, make the situation of composition compares with melting mixing fluorine resin powder coating raw material, easily homogeneous mixes, and the few fluorine resin powder with solidified nature functional group of paint film defect and the manufacture method of coating composition thereof.
Background technology
Because with poly-inclined to one side 1, the 1-difluoroethylene is the decentralized thermoplastic fluorine-containing cold coating of principal constituent, be that the erosion resistance of filming, weather resistance and the easy deciduous of dirt etc. of the solvable type thermoset of solvent fluorine resin paints of principal constituent are good with the multipolymer of fluoroolefin and vinyl ether or vinyl ester, so be widely used in recent years protection against corrosion with, paint field such as for building, industrial (for example, with reference to the special public clear 60-21667 of Japanese Patent, spy open clear 59-102962, the spy opens clear 61-57609 etc.).
In addition, at serious environmental pollution problem day by day, the common powder fluorine resin paints of low public hazards type (for example, open with reference to Japanese patent laid-open 1-103670, spy flat 2-60968, spy open flat 6-345822, the spy opens flat 7-145332 etc.) of the output of minimizing organic solvent (VOC) has been proposed.
The host resin that is generally used for powder coating is with before other additive mixes, in most cases at first from resin solution or dispersion liquid, remove to desolvate and consolidate shapeization (for example, opening flat 8-118357 etc. with reference to the spy) by continous way decompression Desolventizing apparatus or spray drying unit etc.But in this method, have resin to be detained in removing the device that desolvates, if long-time heating, then the generating portion gel particles must carry out the steps such as filtration of this gel particles, and makes coating sometimes and film rerum natura decline.
Then, making under the situation of powder coating composition, the general employing by aforesaid method carried out coarse reduction after to host resin desolventizing, dried sneak into solidifying agent and various additive after, through melting mixing, pulverize once more, method that grading system gets coating composition.Owing to adopted the rapid manufacture method of such multistep, compare the problem that exists manufacturing cost to improve with solvent based coating.In order to address this problem, attempt by dissolving in the modulation solution or be dispersed with the material solution of host resin as raw material, solidifying agent, various additives, removing then desolvates directly obtains powder coating.
For example, the Japanese Patent spy opens and has disclosed among the 2000-34426 by using the such low boiling point solvent of methyl alcohol, after mixing additives such as the host resin that adopts in the general powder coating such as acrylic resin and solidifying agent thereof, spraying drying or supply to continous way decompression Desolventizing apparatus, remove volatile component, obtain the method for powder coating.
But the present inventor finds, the fluorine resin with solidified nature functional group and acrylic resin etc. are different, even use lower boiling solvent also to have problems.Promptly, the 1st, in fact the remaining unreacted monomer of higher in the solution after the polymerization desolvates so utilize spraying drying or continous way decompression Desolventizing apparatus to remove under low like this temperature, and existence can't reach the problem as the enough solid formation branch concentration of powder coating.The 2nd, and if remove under than higher temperature and desolvate in order to improve above-mentioned solid the branchs concentration that forms, even then under the temperature that does not cause curing reaction, also exist and the problem of same generation gel particles during above-mentioned host resin desolventizing.
The present invention 1 purpose is to solve to make fluorine resin solution or the dispersion liquid desolventizing with solidified nature functional group, form the host resin of powder coating composition, coating additive such as dry blending solidifying agent then, the foregoing problems that occurs when making powder coating composition.The present invention 2 purpose is to solve dissolving in the modulation solvent or disperseed to have fluorine resin, the solidifying agent of solidified nature functional group, the material solution of various additives, utilize continous way decompression Desolventizing apparatus to remove and desolvate the foregoing problems that occurs when directly making powder coating.
The announcement of invention
The present invention is the invention of finishing in order to solve foregoing problems.The present invention 1 provides the manufacture method of the fluorine resin powder with solidified nature functional group, the feature of this method is, in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid, add anti-gelating agent (B) and mix, then this solution or dispersion liquid are supplied to the film vacuum-evaporator unit, from this solution or dispersion liquid, remove and desolvate.The present invention 2 provides the manufacture method of the fluorine resin powder coating composition with solidified nature functional group, the feature of this method is, other powder coating that adds anti-gelating agent (B), solidifying agent (C) and add as required in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid is with additive (D) and mix, obtain resin combination solution or dispersion liquid, then this solution or dispersion liquid are supplied to the film vacuum-evaporator unit, from this resin combination solution or dispersion liquid, remove and desolvate.
The best mode that carries out an invention
Below, better embodiment of the present invention is elaborated.
(fluorinated copolymer (A))
At first, the fluorinated copolymer with solidified nature functional group (A) in the used powder coating raw material of manufacture method of the present invention is described.
This fluorinated copolymer (A) has solidified nature functional group, is preferably the fluoropolymer that employing is made of following polymerized unit.
(a) 35～99 moles of % of fluoroolefin
(b) has 1～30 mole of % of monomer of solidified nature functional group
(c) but 0～64 mole of % of the monomer of other copolymerization
Be more preferably the fluorinated copolymer that employing is made of following polymerized unit.
(a) 35～65 moles of % of fluoroolefin
(b) has 1～30 mole of % of monomer of solidified nature functional group
(c) but 20～60 moles of % of the monomer of other copolymerization
The fluoroolefin of above-mentioned (a) can adopt a kind also can be used in combination more than 2 kinds.If fluoroolefin lacks than above-mentioned, then weathering resistance descends, if more than above-mentioned, the composition heterogeneity of multipolymer then, the rerum natura of filming descends.In addition, if the monomer with solidified nature functional group (b) lacks than above-mentioned, then solidify and can not fully carry out, if compare too much with above-mentioned scope, the weathering resistance of then filming descends, and paint film defect increases.In addition, but if the monomer of other copolymerization (c) is too much, membranous declines such as the weathering resistance of then filming.(c) but lower value is 0% to be meant the monomeric situation that does not contain this copolymerization fully.
Among the present invention, (a) fluoroolefin is preferably the fluoroolefin of the carbonatoms about 2～4 of contain fluorine atoms such as trifluoro-ethylene, trifluorochloroethylene, tetrafluoroethylene, trifluoro propene, tetrafluoeopropene, vinylidene fluoride, five fluorine propylene, R 1216, tetrafluoro butylene, five fluorine butylene.Wherein, be more preferably trifluoro-ethylene, trifluorochloroethylene, tetrafluoroethylene, vinylidene fluoride, R 1216.In addition, except that fluorine atom, can also contain other halogen atoms such as chlorine atom simultaneously.
The monomer with solidified nature functional group to (b) is not particularly limited, and can exemplify (i) hydroxyl of having as solidified nature functional group, the (ii) carboxyl or the (iii) monomer etc. of group such as epoxy group(ing).
Have the monomeric example of hydroxyl as (i), can exemplify 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-cyclohexyl vinyl ether, 1-hydroxymethyl-4-vinyl methylol hexanaphthene, Ba Dousuan 2-hydroxy methacrylate, 2-hydroxyethyl allyl ethers, vinyl carbinol, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester etc.
As the monomeric example that (ii) has carboxyl, but unsaturated fatty acidss such as exemplified by acrylic, methacrylic acid, Ba Dousuan, iso-crotonic acid, 10-undecylenic acid, 9-octadecenoic acid (oleic acid), fumaric acid, toxilic acid etc. have the monomer of carboxyl, or the monomer that contains carboxyl of following formula (1), (2) expression etc.
(1)CH 2＝CHOR 1OCOR 2COOM
(2)CH 2＝CHCH 2OR 3OCOR 4COOM
In the formula, R 1, R 3Be the bivalent hydrocarbon radical of carbonatoms 2～15, R 2, R 4Be saturated or undersaturated straight chain shape or cyclic bivalent hydrocarbon radical, M is the compound that contains hydrogen atom, alkyl, basic metal or nitrogen-atoms.
Wherein, the copolymerization of 10-undecylenic acid and fluoroolefin is good, and is more satisfactory.
These have the directly copolymerization of monomer of carboxyl.In addition, under the situation that makes the monomer copolymerization of difficult copolymerization under the acid atmosphere such as vinyl ether, carboxyl carries out pickling and changes carboxyl again into form blocks such as an alkali metal salts during polymerization after the polymerization.
In addition, available monomer with hydroxyl obtains multipolymer, makes the such multi-anhydride of succinyl oxide and this copolymer reaction, makes it be modified as the multipolymer with carboxyl.
As the monomeric example that (iii) has epoxy group(ing), can exemplify Racemic glycidol vinyl ether, Racemic glycidol allyl ethers, Racemic glycidol (methyl) acrylate etc.
In addition, spendable (c) but the monomer of other copolymerization can exemplify vinyl-acetic ester, propionate, vinyl butyrate, the trimethylacetic acid vinyl acetate, vinyl caproate, sad vinyl acetate, vinyl esters such as hard vinyl acetate ester, methylvinylether, ethyl vinyl ether, isopropyl-ethylene base ether, n-propyl vinyl ether, n-butyl vinyl ether, tert-Butyl vinyl ether, IVE, vinyl ethers such as cyclohexyl vinyl ether, the methyl isopropyl alkene ether, the ethyl isopropenyl ethers, the isopropyl propenyl ether, the n-propyl isopropenyl ethers, the normal-butyl isopropenyl ethers, tertiary butyl isopropenyl ethers, the isobutyl-isopropenyl ethers, pseudoallyl ethers such as cyclohexyl isopropenyl ethers, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) vinylformic acid peopentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) Isohexyl acrylate, (methyl) 2-EHA, (methyl) esters of acrylic acids such as (methyl) lauryl acrylate, methyl crotonate, the iso-crotonic acid methyl esters, ethyl crotonate, the iso-crotonic acid ethyl ester, the Ba Dousuan n-propyl, the Ba Dousuan isopropyl ester, isobutyl crotonoate, the Ba Dousuan tert-butyl ester, the just own ester of Ba Dousuan, crotonate classes such as Ba Dousuan dissident ester, ethyl allyl ether, the propyl group allyl ethers, the butyl allyl ethers, allyl ether series such as isobutyl-allyl ethers, ethene, propylene, iso-butylene, the 1-hexene, olefines such as tetrahydrobenzene etc.By these monomers of suitable use, can improve and the intermiscibility of solidifying agent and the flexibility of filming etc.
Adopt appropriate means such as emulsion polymerization, solution polymerization, suspension polymerization to make the monomer polymerization of above-mentioned (a)～(c), form the dispersion liquid (aqueous liquid dispersion etc.) or the solution of fluorinated copolymer, thereby obtain solution or the dispersion liquid with fluorinated copolymer (A) of solidified nature functional group of the present invention.
For example, under the situation of emulsion polymerization, as polymerization starter, can adopt common radical initiator, good especially is water soluble starter.Specifically comprise redox initiator that reductive agents such as persulphates such as ammonium persulphate, hydrogen peroxide or they and sodium bisulfite, Sulfothiorine combine etc.
The consumption of polymerization starter can be made appropriate change according to kind, emulsion polymerization condition etc.Usually need the monomer of emulsion polymerization corresponding to 100 mass parts, its consumption is preferably about 0.005～0.5 mass parts.These polymerization starters can add together also and can separately add.
PH with the raising emulsification is a purpose, can adopt pH to adjust agent.Adjust agent as pH and can exemplify organic bases such as mineral alkali such as yellow soda ash, salt of wormwood, former sodium hydrogen phosphate, Sulfothiorine and triethylamine, trolamine, dimethylethanolamine, diethylethanolamine etc.
The emulsion polymerization starting temperature is done suitably decision according to the kind of polymerization starter.Be generally 0～100 ℃, good especially is about 10～90 ℃.Polymerization temperature is about 20～120 ℃.Polymerization pressure can suitably be selected, and is generally 0.1～10MPa, adopts about 0.2～5MPa especially.
Can adopt pack into the together method of reactor of whole monomers, the method for the full dose of packing into continuously, the method for the full dose of separately packing into, the part of packing into make polyreaction begin back, rest parts separately or the whole bag of tricks such as method of packing into continuously.
(anti-gelating agent (B))
Below, anti-gelating agent (B) is described.
Of the present invention have the fluorinated copolymer (A) of solidified nature functional group if general not fusion solidifying agent etc. just can not cause gelation when heating concentrates.But, according to present inventor's discovery, when unexpectedly utilizing the film vacuum-evaporator unit to make powder coating, also gelation can take place under the drying temperature (for example, the drying temperature below 160 ℃) that can not cause gelation usually.
The present invention be directed to the invention that this new problem is finished.One of feature of the present invention is to add to mix anti-gelating agent (B) in the solution of fluorinated copolymer (A) or dispersion liquid.Two of feature of the present invention is to add to mix anti-gelating agent (B), solidifying agent (C) and other powder coating additive (D) in the solution of fluorinated copolymer (A) or dispersion liquid.
The preferably following compound of anti-gelating agent (B) that the present invention is used.
2,6-di-tert-butyl-4-methy phenol (BHT), Octadecane base-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 1,6-hexa-methylene two [(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2,4,6-three decyl phenol, the 4-tert.-butyl phenol, the 4-nonylphenol, 3, the 5-dinonyl phenol, the 4-cyclohexylphenol, the 4-phenylphenol, the 4-octyl phenol, phenol, cresols, 2, the 3-xylenol, the 4-butylphenol, 4-isopentyl phenol, the 4-ethylphenol, the 4-isopropyl-phenol, 4-(2-ethylhexyl) phenol, 4-(1,1-dimethyl heptyl) phenol, 4-decyl phenol, 4-(1,1-dimethyl hexyl) phenol, 4-isohexyl phenol, 4-octadecyl phenol, 3, the 5-diisobutyl phenol, 3,5-diamyl phenol, 1, phenols such as 3-diphenylol propane.
Epoxidised soybean oil, epoxidized linseed, epoxidation tung oil, epoxidation fish oil, epoxidation Viscotrol C, epoxidation Thistle oil, epoxy methyl stearate, three-glycidyl isocyanuric acid ester, 3-(2-biphenylyloxy)-1,2-propylene oxide, epoxidized polybutadiene, bisphenol A diglycidyl ether, 3-vinyl cyclohexene diepoxide, Dicyclopentadiene (DCPD) diepoxide, 3, epoxy compoundss such as the alkyl esters of 4-epoxy-cyclohexane carboxylic acid, two (3,4-epoxy group(ing) cyclohexyl) adipic acid ester.
Triphenyl phosphite, the tricresyl phosphite monooctyl ester, trilauryl phosphite, tridecyl phosphite, phosphorous acid octyl group diphenyl ester, triisodecyl phosphite ester, phosphorous acid phenyl isodecyl ester, phosphorous acid phenyl two (three last of the ten Heavenly stems ester), the different monooctyl ester of phosphorous acid phenylbenzene, phosphorous acid phenylbenzene ester in the last of the ten Heavenly stems, tricresyl phosphite (nonyl phenyl ester), tricresyl phosphite (2-ethylhexyl), tributyl phosphate, acid phosphorous acid two lauryls, the acid dibutyl phosphite, tricresyl phosphite (dinonyl phenyl ester), trilauryl trithiophosphite, phosphorous acid esters such as trilauryl phosphite.
The oxidation inhibitor of metallic soaps such as above-claimed cpd and Zinc Stearate, calcium stearate, barium stearate, ricinoleic acid calcium, barium laurate and usefulness.
Be called two (2,2,6,6-tetramethyl--4-piperidyl) sebates of HALS for short, 2,2,6,6-tetramethyl--4-piperidyl stearate, 1,2,2,6,6-pentamethyl--4-piperidyl stearate, 2,2,6,6-tetramethyl--4-piperidyl benzoic ether, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, 4-acetoxyl group-2,2,6, the 6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine, 4-acryloxy-2,2,6, the 6-tetramethyl piperidine, 4-(phenyl acetoxyl group)-2,2,6, the 6-tetramethyl piperidine, 4-benzoyloxy group-2,2,6, the 6-tetramethyl piperidine, 4-methoxyl group-2,2,6, the 6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, hindered amines such as 6-tetramethyl piperidine are photostabilizer.
The consumption of these anti-gelating agents (B) is 0.05～15 quality % corresponding to fluorinated copolymer (A), is preferably 0.02～10 quality %, more preferably 0.05～5 quality %.
In addition, also can adopt triazines such as hydroxyphenyltriazinuv class is stablizer, and sulphur such as Tyox B, thio-2 acid two (tetradecyl ester), thio-2 acid two (stearyl), propane thioic acid glycerine tri-n-butyl, propionic acid glycerine three monooctyl esters are stablizer.
Among the present invention,, in the film vacuum-evaporator unit, carry out drying, the gelation of the fluorinated copolymer (A) in the time of can substantially preventing drying by adding this anti-gelating agent (B).Its principle is also not exclusively understood now, may be because be present in the instabilities such as two keys, hydroperoxide, unstable chlorine atom of the trace in the resin structure of multipolymer basic or from polymerization system during separation resin the Unstable Substance of remaining trace etc. can cause the material of gelation, the cause of stabilization because having added above-mentioned anti-gelating agent (B).
(solidifying agent (C))
As being used for solidifying agent of the present invention (C), can exemplify block isocyanate compound, for example, isophorone diisocyanate, 1, polyisocyanate compounds such as hexamethylene-diisocyanate are by block agent blocks such as 6-caprolactone, ethyl methyl ketones and the blocked isocyanate solidifying agent that forms, the urea dione compounds, amide hardener with beta-hydroxyalkylamides base, for example, system PrimidXL-552 of エ system ス Showa Denko K. K or three-glycidyl isocyanuric acid ester (TGIC) solidifying agent etc.They are the solidifying agent by being heating and curing.In addition, be also included within the scope of the present invention by solidified solidifying agent such as ultraviolet rays.The better ratio of the fluorinated copolymer with solidified nature functional group (A) among the present invention/solidifying agent (C) is 40/60～98/2 (quality criteria), and good especially is 50/50～97/3.
Powder coating composition of the present invention is made of fluorinated copolymer (A), anti-gelating agent (B) and solidifying agent (C) basically, but as required, in the scope that does not have influence on purpose of the present invention, also can add other powder coating additive (D).This powder coating can exemplify surface smoothing agent, silane coupling agent, UV light absorber, photostabilizer, tinting pigment, metallic pigment, filler pigment etc. with additive.The resin such as known or known acrylic resin, vibrin, Synolac, aminoresin, Resins, epoxy, urethane resin that also can be used in addition, general coating composition with fluorinated copolymer (A).
(film vacuum-evaporation drying)
Below, film vacuum-evaporation drying step is described.
Among the present invention, method 1 is to add anti-gelating agent (B) and mixing in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid, then this solution or dispersion liquid are supplied in the film vacuum-evaporator unit, from this solution or dispersion liquid, remove and desolvate.As the film vacuum-evaporator unit, can adopt in normally used centrifugal film vacuum-evaporator unit, belt film vacuum-evaporator unit or the spiral shell slurry formula film vacuum-evaporator unit any, be under the full-bodied situation at molten fluoropolymer multipolymer (A) especially, best is the spiral shell slurry formula film vacuum-evaporator unit of easily discharging.Refreshing steel パ Application テ ッ Network Co., Ltd. system) or double-shafted extruder etc. spiral shell slurry formula film vacuum-evaporator unit for example can adopt high viscosity with film vacuum evaporator " エ Network セ バ " (trade(brand)name:.
The method of removing to solvent is not particularly limited, and can adopt the method for decompression, heating or their combination.The method efficient of decompression and heating combination is high especially, can suppress thermal degradation when, so more satisfactory.
As Heating temperature, as long as below the temperature of the boundary that the fluorinated copolymer with solidified nature functional group (A) is stabilized by anti-gelating agent (B) and can be effectively except that more than the temperature of desolvating.Specifically, better be below 180 ℃ and more than 50 ℃.Be more preferably below 160 ℃ and more than 80 ℃.
Among the present invention, method 2 is other powder coating additives (D) that add anti-gelating agent (B), solidifying agent (C) and add as required in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid, mix the back and obtain resin combination solution or dispersion liquid, this solution or dispersion liquid are supplied in the film vacuum-evaporator unit, from this resin combination solution or dispersion liquid, remove and desolvate.
The film vacuum-evaporator unit can adopt said apparatus, and Heating temperature needs only at the substantive curing reaction that does not cause fluorinated copolymer (A) and solidifying agent (C) and makes in the dry temperature range of fully carrying out.For example, adopt under the situation of blocked isocyanate solidifying agent, Heating temperature is below 160 ℃, adopt under the situation of TGIC, Heating temperature adopts under the situation of the amide hardener with beta-hydroxy below 110 ℃, and Heating temperature is below 140 ℃ and more than 50 ℃.
(mixing pulverizing)
Below, mixing pulverising step is described.
Among the present invention, method 1 is after utilizing high-speed mixer (Henschel mixing machine) etc. that fluorinated copolymer (A), anti-gelating agent (B), solidifying agent (C) and other powder coating of adding are as required mixed (do and mix) with each composition of additive (D) with pulverulence, pushes mixing roll etc. with single shaft or twin shaft and carries out melting mixing.The extruding built-in temperature is in the temperature range of the above-mentioned substantive curing reaction that does not cause fluorinated copolymer (A) and solidifying agent (C).The mixing thing of abundant melting mixing is squeezed into sheet etc., cools off this extrudate, at room temperature pulverize.Size-grade distribution after the pulverizing is 20～50 μ m when being used to spray, and is 70～120 μ m when being used for flowing dip-coating.
Among the present invention, method 2 is other powder coating additives (D) that add anti-gelating agent (B), solidifying agent (C) and add as required in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid, mix the back and obtain resin combination solution or dispersion liquid, this solution or dispersion liquid are supplied in the film vacuum-evaporator unit, to from this resin combination solution or dispersion liquid, remove the mixing thing that desolvates and obtain then and be squeezed into sheet etc., cool off this extrudate, at room temperature pulverize.In this case, the fluorine resin powder coating composition just can obtain by a step, can be described as extremely simple manufacturing step.
As mentioned above, after the curable fluorine-containing resin powder coating composition of the present invention that utilizes the film vacuum-evaporator unit to obtain is coated on base material as object, carries out the heat treated calcining and make it solidify to form application to film.
Coating process is not particularly limited, can adopts known or known in the past method, for example, electrostatic spraying (spraying), the dip-coating etc. of flowing.Application thickness is not particularly limited, and coating thickness is 30～120 μ m usually.Heat treated temperature (solidification value) is 140～220 ℃, is preferably about 150～200 ℃, and the heat treated time is 10～60 minutes, is preferably about 15～30 minutes.
Base material as the object of coating composition of the present invention can exemplify iron plate, stainless steel, aluminium, steel plate galvanized etc.These substrate surfaces can pass through Plessy's green processing, zinc phosphate processing, chromic salt gloss finish etc. in advance.
Embodiment
Below, by synthesis example and embodiment the present invention is specifically described, but the present invention is not limited in these explanations.Umber in following examples is represented mass parts if no special instructions, and % represents quality %.
Synthesis example 1
Have pack in the pressure vessel (withstand voltage 5.0MPa) of the stirrer IVE (iBVE) of the dimethylbenzene of 26.2kg, the cyclohexyl vinyl ether of 2.7kg (CHVE), 1.5kg, the 4-hydroxybutyl vinyl ether (HBVE) of 4.2kg, the salt of wormwood of 0.17kg and the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester (PBPV) of 0.01kg at the stainless steel of inner capacities 50L, remove the molten oxygen of depositing by the curing degassing of liquid nitrogen.
Then, import the trifluorochloroethylene (CTFE) of 8.3kg, slowly heat up.Temperature maintenance is under agitation continued reaction on one side on 65 ℃ of one side, water-cooled makes the reactor stopped reaction after 10 hours.After being cooled to room temperature, remove unreacted monomer, open reactor.Gained reaction solution diatomite filtration is removed solid substance.
Synthesis example 2～6
Carry out the polymerization except changing monomeric composition according to composition shown in the table 1, other operation is identical with synthesis example 1.
Table 1
Synthesis example ?1 ?2 ?3 ?4 ?5 ?6
Monomer is formed (mole %) ?CTFE ?50 ?51 ?50 ?50
?TFE ?45 ?45
?CHVE ?15 ?25 ?45 ?10 ?15 ?15
?EVE ?12
?iBVE ?10 ?10
Vinyl benzoate ?15 ?10 ?5
?Veova10 ?15 ?10 ?5
?HBVE ?25 ?12 ?10 ?15
?GVE ?15
Undecylenic acid ?15
Divide concentration (%) Gu form ?39 ?38 ?40 ?38 ?39 ?41
Fluorinated copolymer solution ?A-1 ?A-2 ?A-3 ?A-4 ?A-5 ?A-6
(notes) TFE: tetrafluoroethene CTE: CTFE CHVE: cyclohexyl vinyl ether EVE: ethyl vinyl ether iBVE: IVE HBVE:4-hydroxybutyl vinyl ethers GVE: glycidol vinyl ethers
Embodiment 1
As shown in table 2, in fluorinated copolymer solution (A-1) 30kg that synthesis example 1 obtains, add tridecyl phosphite and the mixing of 8.4g.Then, with 30kg/ hour feed speed, (trade(brand)name: input port refreshing steel パ Application テ ッ Network Co., Ltd. system) supplied to this solution in this device from film vacuum-evaporator unit " エ Network セ バ ".Vacuum tightness in the device is that 95 ℃, the stirring revolution of film vacuum-evaporator unit are that the stirring revolution that 400rpm, molten resin are discharged with the spiral shell slurry is 300rp for-0.09MPa (gauge pressure), heat medium temperature.The nonvolatile component concentration of having removed the curing fluorinated copolymer of solvent is 99.5%.This solid fluorine-containing multipolymer is called as (A '-1).
Then, with dry-mixed machine (high-speed mixer of Mitsui chemical machinery Co., Ltd. system), powder to the above-mentioned solid fluorine-containing multipolymer of 137g (A '-1), 15.0g ア ダ Network ト B1530 (trade(brand)name: ヒ ュ Le ズ Co., Ltd. system 6-caprolactone blocked isocyanate solidifying agent), 0.5g モ ダ Off ロ-2000 (trade(brand)name: モ Application サ Application ト Co., Ltd. system is coated with flat agent), 0.5g bitter almond oil camphor and the titanium dioxide of 30g carry out about 1 minute mixing, under 90～130 ℃ temperature condition, extrude then, with mixing roll (trade(brand)name: プ ス コ ニ-ダ-PR-46, プ ス Co., Ltd. system) melting mixing.The component proportions of this molten mixture is as shown in table 3.
After this molten mixture is cooled to 20 ℃, pulverize, sieve acquisition curable fluorine-containing resin powder coating composition with the metallic screen of 180 sieve meshes with the impact type hammer mill.
The gained powder coating composition is applied on the steel plate of handling through zinc phosphate by electrostatic coating, it was solidified 20 minutes, obtain to film.
The gained coating and the rerum natura of filming are carried out following mensuration, and its result is as shown in table 4.
[anti-anti-caking]
According to following benchmark to estimating at the coating of 40 ℃ of storages after 7 days.
Zero: do not lump △ fully: a small amount of caking is arranged, but easily disintegration revert to Powdered, *: it is more to lump, even reinforcing can not revert to powder yet.
[appearance of film (smoothness)]
Zero: no any unusual, △: visible a small amount of concavo-convex point, *: the concavo-convex point of visible a great deal of.
[gloss (60 °)]
Measure according to JIS K5400 7.6.
Embodiment 2～6
Similarly to Example 1, from the fluorinated copolymer solution A-2～A-6 shown in the table 2, remove and desolvate, obtain solid fluorine-containing copolymer A '-2～A '-6.Then, make the powder coating composition of ratio shown in the table 3 similarly to Example 1, similarly to Example 1, the application said composition, it the results are shown in table 4.
Comparative example 1～2
In synthesis example 4～synthesis example 5, do not add anti-gelating agent among the fluorinated copolymer solution A-4～A-5 of gained, remove similarly to Example 1 and desolvate, obtain solid fluorine-containing copolymer A '-7～A '-8.Then, make the powder coating composition of ratio shown in the table 3 similarly to Example 1, application said composition similarly to Example 1, its result is as shown in table 4.
Table 2
The raw material name Embodiment Comparative example
??1 ??2 ??3 ??4 ??5 ??6 ??1 ??2
The solid fluorine-containing multipolymer
??A′-1 ??A′-2 ??A′-3 ??A′-4 ??A′-5 ??A′-6 ??A′-7 ??A′-8
Fluorinated copolymer solution ??A-1 ??137
??A-2 ??138
??A-3 ??141
??A-4 ??139 ??139
??A-5 ??137 ??137
??A-6 ??137
Anti-gelating agent Tridecyl phosphite ??0.1 ??0.1 ??0.1
Diphenylol propane ??0.1 ??0.1
??Sanol ??LS744 *1 ??0.1
?? *1:Sanol LS744 (Japanese チ バ ガ ィ ギ Co., Ltd. system hindered amine is a photostabilizer)
Table 3
The raw material name Embodiment Comparative example
??1 ??2 ??3 ??4 ??5 ??6 ??1 ??2
The solid fluorine-containing multipolymer ??A′-1 ??53.4
??A′-2 ??52.4
??A′-3 ??56.4
??A′-4 ??52.8
??A′-5 ??53.4
??A′-6 ??56.2
??A′-7 ??52.8
??A′-8 ??56.2
Solidifying agent ??アダクト ??B-1530 ??15.0 ??15.0 ??15.0 ??15.0 ??15.0
??アダクト ??BF-1540 *2 ??15.0
The bay diacid ??5.6
??TGIC ??18.2
Additive ??モダフロ ??-2000 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5
Bitter almond oil camphor ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5
Titanium dioxide ??30 ??30 ??30 ??30 ??30 ??30 ??30 ??30
The application condition Calcining temperature (℃) ??180 ??180 ??180 ??180 ??180 ??180 ??140 ??140
Calcination time (minute) ??20 ??20 ??20 ??20 ??20 ??20 ??20 ??20
?? *2: ア ダ Network ト BF-1540 (the system ウ レ ト ジ オ of ヒ ュ Le ズ Co., Ltd. Application)
Table 4
Embodiment Comparative example
??1 ??2 ??3 ??4 ??5 ??6 ??1 ??2
Anti-anti-caking ??○ ??○ ??○ ??○ ??○ ??○ ??△ ??×
Appearance of film ??○ ??○ ??○ ??○ ??○ ??○ ??× ??×
Gloss ??137 ??120 ??135 ??138 ??129 ??120 ??108 ??110
Embodiment 7
All the components homogeneous with the composition that made table 5 illustrated embodiment 7 in 1 hour mixes formation solution.Then, with 30kg/ hour feed speed, (trade(brand)name: input port refreshing steel パ Application テ ッ Network Co., Ltd. system) supplied to this resin combination solution in this device from film vacuum-evaporator unit " エ Network セ バ ".Vacuum tightness in the device is that 95 ℃, the stirring revolution of film vacuum-evaporator unit are that the stirring revolution that 400rpm, molten resin are discharged with the spiral shell slurry is 300rp for-0.09MPa (gauge pressure), heat medium temperature.The nonvolatile component concentration of gained curable resin composition is 99.5%.
After this solid resinous composition is cooled to 20 ℃, pulverize with the impact type hammer mill, the metallic screen with 180 sieve meshes sieves again, acquisition curable fluorine-containing resin powder coating composition.The gained powder coating composition is applied on the steel plate of handling through zinc phosphate by electrostatic coating, it was solidified 20 minutes, obtain to film.
Similarly to Example 1, the gained coating and the rerum natura of filming are measured, its result is as shown in table 6.
Embodiment 8～12, comparative example 3～4
Under condition similarly to Example 7, obtain powder coating composition by the fluorinated copolymer composition (solution) shown in the table 5, carry out application with said composition similarly to Example 7.It the results are shown in table 6.
Table 5
The raw material name Embodiment Comparative example
??7 ??8 ??9 ??10 ??11 ??12 ??3 ??4
Fluorinated copolymer solution ??A-1 ??137
??A-2 ??138
??A-3 ??141
??A-4 ??139 ??137
??A-5 ??137 ??138
??A-6 ??137
Anti-gelating agent Tridecyl phosphite ??0.1 ??0.1 ??0.1
Diphenylol propane ??0.1 ??0.1
??Sanol?LS744 ??0.1
Solidifying agent ??アダクトB-1530 ??15.0 ??15.0 ??15.0 ??15.0 ??15.0
??アダクトBF-1540 ??15.0
The bay diacid ??5.6
??TGIC ??18.2
Additive ??モダフロ-2000 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5
Bitter almond oil camphor ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5
Titanium dioxide ??30 ??30 ??30 ??30 ??30 ??30 ??30 ??30
The application condition Calcining temperature (℃) ??180 ??180 ??180 ??180 ??180 ??180 ??140 ??140
Calcination time (minute) ??20 ??20 ??20 ??20 ??20 ??20 ??20 ??20
Table 6
Embodiment Comparative example
7 ?8 ?9 ?10 ?11 ?12 ?3 ?4
Anti-anti-caking ○ ?○ ?○ ?○ ?○ ?○ ?△ ?×
Appearance of film ○ ?○ ?○ ?○ ?○ ?○ ?× ?×
Gloss 136 ?119 ?136 ?137 ?129 ?121 ?107 ?111
The possibility of utilizing on the industry
Utilize the present invention, passing through under the higher temperature conditions in the situation of film vacuum vaporising device desolventizing even can obtain, also be difficult to cause the gelation of resin, in addition, the easy homogeneous of composition mixes, and few fluorine-containing attached cosmetics body and the coating composition thereof with curing property functional group of paint film defect.

Claims (5)

1. the manufacture method that has the fluorine resin powder of solidified nature functional group, it is characterized in that, in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid, add anti-gelating agent (B) and mix, then this solution or dispersion liquid are supplied to the film vacuum-evaporator unit, from this solution or dispersion liquid, remove and desolvate.
2. the manufacture method that has the fluorine resin powder coating composition of solidified nature functional group, it is characterized in that, other powder coating that adds anti-gelating agent (B), solidifying agent (C) and add as required in the solution of the fluorinated copolymer with solidified nature functional group (A) or dispersion liquid is with additive (D) and mix, obtain resin combination solution or dispersion liquid, then this solution or dispersion liquid are supplied to the film vacuum-evaporator unit, from this resin combination solution or dispersion liquid, remove and desolvate.
3. manufacture method as claimed in claim 1 or 2, its feature also be, the solidified nature functional group of fluorinated copolymer (A) is selected from hydroxyl, carboxyl and epoxy group(ing) at least a kind.
4. as each described manufacture method in the claim 1～3, its feature also is, anti-gelating agent (B) is at least a kind of photostabilizer for being selected from phenols, epoxy compounds, phosphorous acid esters and hindered amine.
5. as each described manufacture method in the claim 2～4, its feature is that also the temperature when solvent is removed is the temperature that does not cause the curing reaction of fluorinated copolymer (A) and solidifying agent (C) in fact.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104704013A (en) * 2012-10-03 2015-06-10 旭硝子株式会社 Method for producing fluorine-containing copolymer solution, and coating composition
CN104927505A (en) * 2015-06-18 2015-09-23 巨化集团技术中心 Thermoset fluororesin powder coating preparation method
CN107922784A (en) * 2015-07-01 2018-04-17 日本涂料控股有限公司 The strippable compelx coating of superficial layer, the coating composition for forming compelx coating and method
CN108602922A (en) * 2015-11-20 2018-09-28 霍尼韦尔国际公司 Fluorinated copolymer for coating application

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200301264A (en) * 2001-12-19 2003-07-01 Asahi Glass Co Ltd Processes for production of powdered fluorine containing resins with curable functional groups and coating compositions containing the same
WO2007132736A1 (en) * 2006-05-11 2007-11-22 Asahi Glass Company, Limited Powder coating composition
EP2076566B1 (en) * 2006-10-13 2011-08-31 3M Innovative Properties Company Powder coating fluoropolymer compositions containing mono-hydroxy aromatic materials
KR101642518B1 (en) * 2010-03-29 2016-07-26 삼성전기주식회사 Composition for forming Board and Printed Circuit Board using the same
EP2735582B1 (en) * 2011-07-19 2016-04-06 Asahi Glass Company, Limited Method for producing ethylene-tetrafluoroethylene copolymer powder
US9624325B2 (en) 2011-10-05 2017-04-18 Honeywell Intenational Inc. Curable fluorocopolymer formed from tetrafluoropropene
US10435580B2 (en) 2015-11-20 2019-10-08 Honeywell International Inc. Gloss retentive fluorocopolymers for coating applications
MX2016005089A (en) * 2013-10-22 2016-07-19 Honeywell Int Inc Curable fluorocopolymer formed from tetrafluoropropene.
JP2015093953A (en) * 2013-11-13 2015-05-18 旭硝子株式会社 Fluoroolefin copolymer solution, preparation method thereof, and paint composition
WO2015159890A1 (en) * 2014-04-18 2015-10-22 旭硝子株式会社 Powder paint and painted article
US11028199B2 (en) * 2016-10-14 2021-06-08 Daikin Industries, Ltd. Fluoropolymer powder and method for producing same
JP7173003B2 (en) * 2017-06-06 2022-11-16 日本ゼオン株式会社 Cross-linked rubber and method for producing the same

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3758634A (en) 1971-08-16 1973-09-11 Ford Motor Co Ontrol agents and diphenolic crosslinking agents powdered coating composition of unsaturated glycidyl copolymer flow c
CA1047678A (en) 1973-09-06 1979-01-30 Santokh S. Labana Powder coating compositions comprising a copolymer of a glycidyl ester and a dicarboxylic acid crosslinking agent
JPS5157725A (en) 1974-11-18 1976-05-20 Asahi Chemical Ind FUNMATSUTOR YOYOJUSHI SEIBUTSU
US3943082A (en) 1974-12-04 1976-03-09 Union Carbide Corporation Thermosetting powder coatings
JPS59102962A (en) 1982-12-02 1984-06-14 Dainippon Ink & Chem Inc Coating resin composition
JPS6021667A (en) 1983-07-15 1985-02-04 Fujitsu Ltd Scanning light position detecting circuit
JPS6157609A (en) 1984-08-30 1986-03-24 Central Glass Co Ltd Fluorine-containing copolymer
IT1180227B (en) 1984-09-24 1987-09-23 Montefluos Spa PROCESS FOR THE PREPARATION OF LOW MOLECULAR WEIGHT POLYVINYLIDENE FLUORIDE
EP0176347B1 (en) * 1984-09-24 1991-12-18 AUSIMONT S.p.A. Process for preparing vinylidene fluoride homopolymers and its copolymers
JP2535986B2 (en) 1986-12-19 1996-09-18 旭硝子株式会社 Paint composition
DE3874836T2 (en) 1987-07-31 1993-04-29 Nippon Oils & Fats Co Ltd THERMALIZING POWDERED COATING COMPOSITION.
JPH06104792B2 (en) 1987-07-31 1994-12-21 日本油脂株式会社 Thermosetting powder coating composition
KR940001852B1 (en) * 1988-05-31 1994-03-09 이 아이 듀우판 디 네모아 앤드 캄파니 Process for the stabilization of fluoro polymers
JP2782726B2 (en) * 1988-08-29 1998-08-06 大日本インキ化学工業株式会社 Resin composition for powder coating
JP3000645B2 (en) * 1990-09-27 2000-01-17 大日本インキ化学工業株式会社 Method for producing synthetic resin aqueous dispersion
IT1243982B (en) * 1990-10-01 1994-06-28 Ausimont Spa REVERSIBLE GELS BASED ON FLUOROELASTOMERS
DE4040129A1 (en) * 1990-12-15 1992-06-17 Hoechst Ag METHOD FOR PRODUCING A CROSSLINKABLE VARNISH BINDING AGENT FROM FLUOROPOLYMER SOLUTIONS
JPH06345822A (en) 1993-06-11 1994-12-20 Central Glass Co Ltd Fluororesin for powder coating
JPH07145332A (en) * 1993-11-25 1995-06-06 Toagosei Co Ltd Powdery thermosetting coating composition
JPH08118357A (en) * 1994-10-25 1996-05-14 Asahi Glass Co Ltd Recovery of solid fluoroplastic from fluoroplastic solution
GB9508458D0 (en) * 1995-04-26 1995-06-14 Ind Gmbh Crystalline methacrylyl terminated polyesters
JP3500547B2 (en) 1995-06-01 2004-02-23 富士通ディスプレイテクノロジーズ株式会社 Method of manufacturing liquid crystal display panel and liquid crystal display panel
EP0927206A4 (en) * 1997-07-17 2004-11-10 Atofina Chem Inc Fluoropolymer powder coatings from modified thermoplastic vinylidene fluoride based resins
JP2000034426A (en) 1998-07-17 2000-02-02 Mitsubishi Gas Chem Co Inc Preparation of powder coating
TW200301264A (en) * 2001-12-19 2003-07-01 Asahi Glass Co Ltd Processes for production of powdered fluorine containing resins with curable functional groups and coating compositions containing the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104704013A (en) * 2012-10-03 2015-06-10 旭硝子株式会社 Method for producing fluorine-containing copolymer solution, and coating composition
CN104927505A (en) * 2015-06-18 2015-09-23 巨化集团技术中心 Thermoset fluororesin powder coating preparation method
CN107922784A (en) * 2015-07-01 2018-04-17 日本涂料控股有限公司 The strippable compelx coating of superficial layer, the coating composition for forming compelx coating and method
CN107922784B (en) * 2015-07-01 2020-10-30 日本涂料控股有限公司 Composite coating film with strippable surface layer, coating composition for forming composite coating film and method
CN108602922A (en) * 2015-11-20 2018-09-28 霍尼韦尔国际公司 Fluorinated copolymer for coating application

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